Superhard components and powder metallurgy methods of making the same

ABSTRACT

A method of forming a super hard polycrystalline construction comprises forming a liquid suspension of a first mass of nano-ceramic particles and a mass of particles or grains of super hard material having an average particle or grain size of 1 or more microns, dispersing the particles or grains in the liquid suspension to form a substantially homogeneous suspension, drying the suspension to form an admix of the nano-ceramic and super hard grains or particles, and forming a pre-sinter assembly comprising the admix. The pre-sinter assembly is then sintered to form a body of polycrystalline super hard material comprising a first fraction of super hard grains and a second fraction, the nano-ceramic particles forming the second fraction. 
     The super hard grains are spaced along at least a portion of the peripheral surface by one or more nano-ceramic grains, the super hard grains having a greater average grain size than that of the grains in the second fraction which have an average size of less than around 999 nm.

FIELD

This disclosure relates to super hard constructions and methods ofmaking such constructions, particularly but not exclusively toconstructions comprising polycrystalline diamond (PCD) structuresattached to a substrate, and tools comprising the same, particularly butnot exclusively for use in rock degradation or drilling, or for boringinto the earth.

BACKGROUND

Polycrystalline super hard materials, such as polycrystalline diamond(PCD) may be used in a wide variety of tools for cutting, machining,drilling or degrading hard or abrasive materials such as rock, metal,ceramics, composites and wood-containing materials. In particular, toolinserts in the form of cutting elements comprising PCD material arewidely used in drill bits for boring into the earth to extract oil orgas. The working life of super hard tool inserts may be limited byfracture of the super hard material, including by sinning and chipping,or by wear of the tool insert.

Cutting elements such as those for use in rock drill bits or othercutting tools typically have a body in the form of a substrate which hasan interface end/surface and a super hard material which forms a cuttinglayer bonded to the interface surface of the substrate by, for example,a sintering process. The substrate is generally formed of a tungstencarbide-cobalt alloy, sometimes referred to as cemented tungsten carbideand the super hard material layer is typically polycrystalline diamond(PCD), or a thermally stable product TSP material such as thermallystable polycrystalline diamond.

Polycrystalline diamond (PCD) is an example of a super hard material(also called a super abrasive material or ultra hard material)comprising a mass of substantially inter-grown diamond grains, forming askeletal mass defining interstices between the diamond grains. PCDmaterial typically comprises at least about 80 volume % of diamond andis conventionally made by subjecting an aggregated mass of diamondgrains to an ultra-high pressure of greater than about 5 GPa, andtemperature of at least about 1,200° C., for example. A material whollyor partly filling the interstices may be referred to as filler or bindermaterial.

PCD is typically formed in the presence of a sintering aid such ascobalt, which promotes the inter-growth of diamond grains. Suitablesintering aids for PCD are also commonly referred to as asolvent-catalyst material for diamond, owing to their function ofdissolving, to some extent, the diamond and catalysing itsre-precipitation. A solvent-catalyst for diamond is understood be amaterial that is capable of promoting the growth of diamond or thedirect diamond-to-diamond inter-growth between diamond grains at apressure and temperature condition at which diamond is thermodynamicallystable. Consequently the interstices within the sintered PCD product maybe wholly or partially filled with residual solvent-catalyst material.Most typically, PCD is formed on a cobalt-cemented tungsten carbidesubstrate, which provides a source of cobalt solvent-catalyst for thePCD. Materials that do not promote substantial coherent intergrowthbetween the diamond grains may themselves form strong bonds with diamondgrains, but are not suitable solvent—catalysts for PCD sintering.

Cemented tungsten carbide which may be used to form a suitable substrateis formed from carbide particles being dispersed in a cobalt matrix bymixing tungsten carbide particles/grains and cobalt together thenheating to solidify. To form the cutting element with a super hardmaterial layer such as PCD, diamond particles or grains are placedadjacent the cemented tungsten carbide body in a refractory metalenclosure such as a niobium enclosure and are subjected to high pressureand high temperature so that inter-grain bonding between the diamondgrains occurs, forming a polycrystalline super hard diamond layer.

In some instances, the substrate may be fully cured prior to attachmentto the super hard material layer whereas in other cases, the substratemay be green, that is, not fully cured. In the latter case, thesubstrate may fully cure during the HTHP sintering process. Thesubstrate may be in powder form and may solidify during the sinteringprocess used to sinter the super hard material layer.

Ever increasing drives for improved productivity in the earth boringfield place ever increasing demands on the materials used for cuttingrock. Specifically, super hard materials, such as PCD materials, withimproved abrasion and impact resistance are required to achieve fastercut rates and longer tool life.

Cutting elements or tool inserts comprising PCD material are widely usedin drill bits for boring into the earth in the oil and gas drillingindustry. Rock drilling and other operations require high abrasionresistance and impact resistance. One of the factors limiting thesuccess of the polycrystalline diamond (PCD) abrasive cutters is thegeneration of heat due to friction between the PCD and the workmaterial. This heat causes the thermal degradation of the diamond layer.The thermal degradation increases the wear rate of the cutter throughincreased cracking and spalling of the PCD layer as well as backconversion of the diamond to graphite causing increased abrasive wear.

Methods used to improve the abrasion resistance of a PCD composite oftenresult in a decrease in impact resistance of the composite.

The most wear resistant grades of PCD usually suffer from a catastrophicfracture of the cutter before it has worn out. During the use of thesecutters, cracks grow until they reach a critical length as whichcatastrophic failure occurs, namely, when a large portion of the PCDbreaks away in a brittle manner. These long, fast growing cracksencountered during use of conventionally sintered PCD, result in shorttool life.

Furthermore, despite their high strength, polycrystalline diamond (PCD)materials are usually susceptible to impact fracture due to their lowfracture toughness. Improving fracture toughness without adverselyaffecting the material's high strength and abrasion resistance is achallenging task.

There is therefore a need for a super hard composite such as a PCDcomposite that has good or improved abrasion, fracture and impactresistance and a method of forming such composites.

SUMMARY

Viewed from a first aspect there is provided a method of forming a superhard polycrystalline construction, comprising:

-   -   forming a liquid suspension of a first mass of nano-ceramic        particles and a mass of particles or grains of super hard        material having an average particle or grain size of 1 or more        microns;    -   dispersing the nano-ceramic particles and mass of super hard        particles or grains in the liquid suspension to form a        substantially homogeneous suspension;    -   drying the suspension to form an admix of the nano-ceramic        particles and super hard grains or particles;    -   forming a pre-sinter assembly comprising the admix;    -   treating the pre-sinter assembly in the presence of a        catalyst/solvent material for the super hard grains at an        ultra-high pressure of around 5 GPa or greater and a temperature        to sinter together the grains of super hard material to form a        body of polycrystalline super hard material comprising a first        fraction of super hard grains and a second fraction, the super        hard grains exhibiting inter-granular bonding and defining a        plurality of interstitial regions therebetween;    -   the nano-ceramic particles forming the second fraction; wherein    -   the super hard grains in the first fraction are spaced along at        least a portion of the peripheral surface by one or more        nano-ceramic grains in the second fraction;    -   the super hard grains in the first fraction having a greater        average grain size than the average grain size of the grains in        the second fraction, the average size of the grains in the        second fraction being less than around 999 nm and the average        grain size of the grains of superhard material in the first        fraction being around 1 micron or more.

Viewed from a second aspect there is provided a super hardpolycrystalline construction comprising:

-   -   a body of polycrystalline super hard material comprising a first        fraction of super hard grains and a second fraction of        nano-ceramic material;    -   the super hard grains in the first fraction having a peripheral        surface; wherein    -   the super hard grains in the first fraction are spaced along at        least a portion of their peripheral surface by a plurality of        nano-ceramic grains or clusters of nano-ceramic grains; wherein        the average grain size of the super hard grains in the first        fraction is around 1 micron or more.

BRIEF DESCRIPTION OF THE DRAWINGS

Various versions will now be described by way of example and withreference to the accompanying drawings in which:

FIG. 1 is a perspective view of an example PCD cutter element orconstruction for a drill bit for boring into the earth;

FIG. 2 is a schematic cross-section of a portion of a conventional PCDmicro-structure with interstices between the inter-bonded diamond grainsfilled with a non-diamond phase material;

FIG. 3 is a schematic cross-section of a portion of an example PCDmicro-structure;

FIG. 4 is a plot showing the results of a vertical borer test comparinga conventional PCD cutter element and an example cutter element;

FIG. 5 is a plot showing the results of a vertical borer test comparinga conventional PCD cutter element and two example cutter elements whichcontained residual catalyst binder in the interstitial spaces(unleached): and

FIG. 6 is a plot showing the results of a vertical borer test comparinga conventional PCD cutter element and an example cutter element fromwhich residual catalyst binder in the interstitial spaces had beenremoved (leached).

The same references refer to the same general features in all thedrawings.

DESCRIPTION

As used herein, a “super hard material” is a material having a Vickershardness of at least about 28 GPa. Diamond and cubic boron nitride (cBN)material are examples of super hard materials.

As used herein, a “super hard construction” means a constructioncomprising a body of polycrystalline super hard material. In such aconstruction, a substrate may be attached thereto or alternatively thebody of polycrystalline material may be free-standing and unbacked.

As used herein, polycrystalline diamond (PCD) is a type ofpolycrystalline super hard (PCS) material comprising a mass of diamondgrains, a substantial portion of which are directly inter-bonded witheach other and in which the content of diamond is at least about 80volume percent of the material. As used herein, “interstices” or“interstitial regions” are regions between the diamond grains of PCDmaterial. In some examples of PCD material, interstices between thediamond grains may be at least partly filled with a binder materialcomprising a catalyst for diamond. In some examples of PCD material,interstices or interstitial regions may be substantially or partiallyfilled with a material other than diamond, or they may be substantiallyempty. PCD material may comprise at least a region from which catalystmaterial has been removed from the interstices, leaving interstitialvoids between the diamond grains.

A “catalyst material” for a super hard material is capable of promotingthe growth or sintering of the super hard material.

The term “substrate” as used herein means any substrate over which thesuper hard material layer is formed. For example, a “substrate” as usedherein may be a transition layer formed over another substrate.

As used herein, the term “integrally formed” regions or parts areproduced contiguous with each other and are not separated by a differentkind of material.

An example of a super hard construction is shown in FIG. 1 and includesa cutting element 1 having a layer of super hard material 2 formed on asubstrate 3. The substrate 3 may be formed of a hard material such ascemented tungsten carbide. The super hard material 2 may be, forexample, polycrystalline diamond (PCD), or a thermally stable productsuch as thermally stable PCD (TSP). The cutting element 1 may be mountedinto a bit body such as a drag bit body (not shown) and may be suitable,for example, for use as a cutter insert for a drill bit for boring intothe earth.

The exposed top surface of the super hard material opposite thesubstrate forms the cutting face 4, also known as the working surface,which is the surface which, along with its edge 6, performs the cuttingin use.

At one end of the substrate 3 is an interface surface 8 that forms aninterface with the super hard material layer 2 which is attached theretoat this interface surface. As shown in the example of FIG. 1, thesubstrate 3 is generally cylindrical and has a peripheral surface 14 anda peripheral top edge 16.

The super hard material may be, for example, polycrystalline diamond(PCD) and the super hard particles or grains may be of natural orsynthetic origin.

The substrate 3 may be formed of a hard material such as a cementedcarbide material and may be, for example, cemented tungsten carbide,cemented tantalum carbide, cemented titanium carbide, cementedmolybdenum carbide or mixtures thereof. The binder metal for suchcarbides suitable for forming the substrate 3 may be, for example,nickel, cobalt, iron or an alloy containing one or more of these metals.Typically, this binder will be present in an amount of 10 to 20 mass %,but this may be as low as 6 mass % or less. Some of the binder metal mayinfiltrate the body of polycrystalline super hard material 2 duringformation of the compact 1,

As shown in FIG. 2, during formation of a conventional polycrystallinecomposite construction, the diamond grains are directly inter-bonded toadjacent grains and the interstices 24 between the grains 22 of superhard material such as diamond grains in the case of PCD may be at leastpartly filled with a non-super hard phase material. This non-super hardphase material, also known as a filler material, may comprise residualcatalyst/binder material, for example cobalt, nickel or iron. Thetypical average grain size of the diamond grains 22 is larger than 1micron and the grain boundaries between adjacent grains is thereforetypically between micron-sized diamond grains, as shown in FIG. 2.

The working surface or “rake face” 4 of the polycrystalline compositeconstruction 1 is the surface or surfaces over which the chips ofmaterial being cut flow when the cutter is used to cut material from abody, the rake face 4 directing the flow of newly formed chips. Thisface 4 is commonly also referred to as the top face or working surfaceof the cutting element as the working surface 4 is the surface which,along with its edge 6, is intended to perform the cutting of a body inuse. It is understood that the term “cutting edge”, as used herein,refers to the actual cutting edge, defined functionally as above, at anyparticular stage or at more than one stage of the cutter wearprogression up to failure of the cutter, including but not limited tothe cutter in a substantially unworn or unused state.

As used herein, “chips” are the pieces of a body removed from the worksurface of the body being cut by the polycrystalline compositeconstruction 1 in use.

As used herein, a “wear scar” is a surface of a cutter formed in use bythe removal of a volume of cutter material due to wear of the cutter. Aflank face may comprise a wear scar. As a cutter wears in use, materialmay progressively be removed from proximate the cutting edge, therebycontinually redefining the position and shape of the cutting edge, rakeface and flank as the wear scar forms.

FIG. 3 is a cross-section through an example of polycrystalline superhard material forming the super hard layer 2 of FIG. 1 showing,schematically, the microstructure. The polycrystalline materialcomprises a first phase dispersed in the super hard phase 40 andcomprising super hard grains 40 spaced by a second phase comprisingnano-sized particles or clusters of particles 42 formed of a ceramicmaterial that, in some examples, may not chemically react with the superhard grains, and/or not inter-grow. Residual catalyst/binder phase 43may be disposed between the first and second phases 40, 42. The secondphase 42 may comprise, for example, any one or more of an oxidematerial, a carbide material, alumina, zirconia, yttria, silica,tantalum oxide, cBN, PCBN, boron nitride, tungsten carbide, hafniumcarbide, zirconium carbide, silicon carbide, silicon nitride or anycombination thereof. The grain size of the dispersed second phaseparticles 42 may, in some examples, be less than around 999 nm, and insome examples 100 nm or less, and/or in the examples comprising clustersof ceramic particles, the average size of the clusters of nano-sizedparticles may be, for example around 5 microns or less and in someexamples, around 500 nm or less.

In some examples, these dispersed second phase particles 42 may belocalized inside the binder pools or in between the grains of the superhard particles, depending on the respective sizes.

The grains of super hard material may be, for example, diamond grains orparticles. In the starting mixture prior to sintering they may be, forexample, bimodal, that is, the feed comprises a mixture of a coarsefraction of diamond grains and a fine fraction of diamond grains. Insome examples, the coarse fraction may have, for example, an averageparticle/grain size ranging from about 10 to 60 microns. By “averageparticle or grain size” it is meant that the individual particles/grainshave a range of sizes with the mean particle/grain size representing the“average”. The average particle/grain size of the fine fraction is lessthan the size of the coarse fraction. For example, the fine fraction mayhave an average grain size of between around 1/10 to 6/10 of the size ofthe coarse fraction, and may, in some examples, range for examplebetween about 0.1 to 20 microns.

In some examples, the weight ratio of the coarse diamond fraction to thefine diamond fraction may range from about 50% to about 97% coarsediamond and the weight ratio of the fine diamond fraction may be fromabout 3% to about 50%. In other examples, the weight ratio of the coarsefraction to the fine fraction may range from about 70:30 to about 90:10.

In further examples, the weight ratio of the coarse fraction to the finefraction may range for example from about 60:40 to about 80:20.

In some examples, the particle size distributions of the coarse and finefractions do not overlap and in some examples the different sizecomponents of the compact are separated by an order of magnitude betweenthe separate size fractions making up the multimodal distribution.

Some examples consist of a wide bi-modal size distribution between thecoarse and fine fractions of super hard material, but some examples mayinclude three or even four or more size modes which may, for example, beseparated in size by an order of magnitude, for example, a blend ofparticle sizes whose average particle size is 20 microns, 2 microns, 200nm and 20 nm.

Sizing of diamond particles/grains into fine fraction, coarse fraction,or other sizes in between, may be through known processes such asjet-milling of larger diamond grains and the like.

In examples where the super hard material is polycrystalline diamondmaterial, the diamond grains used to form the polycrystalline diamondmaterial may be natural and/or synthetic.

In some examples, the binder catalyst/solvent may comprise cobalt orsome other iron group elements, such as iron or nickel, or an alloythereof. Carbides, nitrides, borides, and oxides of the metals of GroupsIV-VI in the periodic table are other examples of non-diamond materialthat might be added to the sinter mix. In some examples, thebinder/catalyst/sintering aid may be Co.

The cemented metal carbide substrate may be conventional in compositionand, thus, may be include any of the Group IVB, VB, or VIB metals, whichare pressed and sintered in the presence of a binder of cobalt, nickelor iron, or alloys thereof. In some examples, the metal carbide istungsten carbide.

The cutter of FIG. 1 according to a first version having themicrostructure of FIG. 3 may be fabricated, for example, as follows.

A mass of hard nano-ceramic particle materials, such as nano cBN, nanotungsten carbide, nano boron carbide, nano silicon carbide, nano siliconnitride having, for example, an average grain size of less than around100 nm, is thoroughly dispersed in a liquid, such as (deionized) wateror an organic solvent, for example ethanol, with or without surfactantsusing a sonication process by inserting an ultrasonic probe into theliquid to form a suspension. Alternatively or in addition, a cluster ofsuch hard nano-ceramic particles may be pre-formed using a conventionalnano precipitation technique and dispersed in such a liquid to form asuspension. The clusters may have, for example, an average size ofaround 5 microns or less, or in some examples around 500 nm or less.Micron sized diamond grits having an average grain size of greater than1 micron are added to the mixture and a sintering agent such as cobaltmay also be added. The mixture is then subjected to a further sonicationprocess by applying the ultrasonic probe into the mixture for a furtherperiod of time to form a homogeneous mixture. The resulting mixture isthen dried using a fast drying process to maintain the homogeneity. Anexample of a suitable technique for drying the suspension is freezedrying using, for example, liquid nitrogen, or spray drying, or spraygranulation to form a substantially homogeneously mixed admix powder inwhich the nano-ceramic particles or clusters are coated on/attached tomicron-sized diamond grits. The admix powder is then sintered underconventional diamond sintering conditions, for example at a pressure ofaround 6.8 GPa, and temperature of around 1300 degrees C., in someexamples with a preformed WC substrate to form a PCD structure such asthat shown in FIG. 3 in which the nano-ceramic particles or clusters 42are located between grain boundaries of the larger diamond grains 40,

Various techniques may be used to achieve this dispersion and homogenousmixture such as ultrasonic dispersing, ball milling, homogenization, andjet milling techniques.

Also, a fast drying process to dry the nano-ceramic/diamond suspensionwithout agglomeration may assist in achieving the desired microstructurein the sintered product. Suitable drying techniques to assist ininhibiting agglomeration of the materials during drying may includefreeze drying, spray freeze drying, spray drying, and spray granulationor spray freeze granulation.

In the example in which a spray drying technique is used, a suitableinlet temperature may be, for example, around 120 deg C., and a suitableoutlet temperature of around 50-56 deg C., and a feeding rate of around5.8 ml/min may be used.

In the example in which a freeze drying technique is used, the admix maybe in the form of a homogeneous paste which is frozen using liquidnitrogen, and is then placed into a freeze dryer for several days untilthe paste is thoroughly dried. The freeze drying conditions may beoptimized for different solvents, for example, for deionized water, thepreferred operation temperature is −55 deg C. plus/minus 5 deg C., andthe preferred pressure is between around 50 to 500 microbar.

In some examples, the catalyst binder such as cobalt may instead beadded to the dried admix powder rather than be included in the liquidsuspension.

In some examples, a stabilizer such as a polymeric stabiliser forexample a surfactant may be added to the suspension mixture. Thesurfactant may be, for example, a non-ionic or cationic surfactant.Also, a binding material such as polyvinyl alcohol may be added to thesuspension mixture to assist in inhibiting agglomeration.

The micron-sized diamond particles or grains may be subjected to a heattreatment or acid treatment prior to adding these to the suspensionmixture to clean the particles or grains by removing impurities. Asuitable heat treatment temperature for micron-sized diamond grits maybe, for example, between around 1000 to around 1300 deg C., or betweenaround 1100 to around 1300 deg C., or between around 1200 to around 1300deg C.

In some examples, the admix material comprising the nano-ceramics andmicron-sized diamond admix, and the carbide material for forming thesubstrate plus any additional sintering aid/binder/catalyst may beapplied as powders and sintered simultaneously in a single UHP/HTprocess. The admix of nano-ceramic and micron sized diamond grains, andmass of carbide powder material are placed in an HP/HT reaction cellassembly and subjected to HP/HT processing. The HP/HT processingconditions selected are sufficient to effect intercrystalline bondingbetween the diamond grains as well as, optionally, the joining ofsintered particles to the cemented metal carbide support. In oneexample, the processing conditions generally involve the imposition forabout 3 to 120 minutes of a temperature of at least about 1200 degreesC. and an ultra-high pressure of greater than about 5 GPa.

In another example, the substrate may be pre-sintered in a separateprocess before being bonded to the polycrystalline material in the HP/HTpress during sintering of the ultrahard polycrystalline material.

In a further example, both the substrate and a body of polycrystallinesuper hard material are pre-formed. The preformed body ofpolycrystalline super hard material is placed in the appropriateposition on the upper surface of the preformed carbide substrate(incorporating a binder catalyst), and the assembly is located in asuitably shaped canister. The assembly is then subjected to hightemperature and pressure in a press, the order of temperature andpressure being again, at least around 1200 degrees C. and 5 GParespectively. During this process the solvent/catalyst migrates from thesubstrate into the body of super hard material and acts as abinder-catalyst to effect intergrowth in the layer and also serves tobond the layer of polycrystalline super hard material to the substrate.

In some examples, the cemented carbide substrate may be formed oftungsten carbide particles bonded together by the binder material, thebinder material comprising an alloy of Co, Ni and Cr. The tungstencarbide particles may form at least 70 weight percent and at most 95weight percent of the substrate. The binder material may comprisebetween about 10 to 50 wt. % Ni, between about 0.1 to 10 wt. % Cr, andthe remainder weight percent comprises Co.

The PCD construction 1 described with reference to FIGS. 1 and 3, may befurther processed after sintering. For example, catalyst material may beremoved from a region of the PCD structure adjacent the working surfaceor the side surface or both the working surface and the side surface.This may be achieved by treating the PCD structure with acid to leachout catalyst material from between the diamond grains, or by othermethods such as electrochemical methods. A thermally stable region,which may be substantially porous, extending a depth of at least about50 microns or at least about 100 microns from a surface of the PCDstructure, may thus be formed which may further enhance the thermalstability of the PCD element.

Furthermore, the PCD body in the structure of FIG. 1 comprising a PCDstructure bonded to a cemented carbide support body may be treated orfinished by, for example, grinding, to provide a PCD element which issubstantially cylindrical and having a substantially planar workingsurface, or a generally domed, pointed, rounded conical orfrusto-conical working surface. The PCD element may be suitable for usein, for example, a rotary shear (or drag) bit for boring into the earth,for a percussion drill bit or for a pick for mining or asphaltdegradation.

In addition, after sintering, the polycrystalline super hardconstructions may be ground to size and may include, if desired, achamfer, for example of around 45 degrees and of approximately 0.4 mmheight measured parallel to the longitudinal axis of the construction.

Some versions are discussed in more detail below with reference to thefollowing examples, which are not intended to be limiting,

EXAMPLE 1

3 g of nano cBN having an average particle size of less than around 100nm was suspended in 15 ml of ethanol and the suspension was treated withsonication probe for at least 15 minutes to thoroughly disperse the nanocBN. In a separate beaker, 1 g of B90 was dissolved into 20 ml ethanol,and then mixed with the nano cBN dispersion. The mixture wasconcentrated to 20 ml by evaporating the excess amount of ethanol in aRotavap. Following the concentration, 5 ml of deionized water wasintroduced into the ethanol concentration and the nano cBN together withB90 was precipitated out of the ethanol solution to form nano clustersof nano cBN.

In a separate beaker, 67.9 g of diamond grains having an average grainsize of around 22 microns (Grade 22) was suspended in 30 ml deionizedwater and the nano clusters of nano cBN solution were then introducedinto the suspension. The mixture was gently stirred with an overheadstirrer for at least half an hour to obtain nano clusters of nano cBNcoated diamond.

In a separate beaker, 2 g of SP cobalt and 1 g of surfactant was mixedwith 20 ml of deionized water, and subjected to a sonication processwith ultrasonic probe for 15 minutes. 29.1 g of diamond grains having anaverage grain size of around 2 microns (Grade 2) was introduced into thesuspension and the suspension was subjected to a sonication process fora further 5 minutes. This suspension was then introduced into thesuspension comprising the diamond grains having an average grain size of22 microns (grade 22) and the resulting mixture was gently stirred withan overhead stirrer for 10 minutes to form a final admix suspension. Thefinal admix suspension was spray dried with a BUCHI Mini-290 spray dryerto remove liquids and form an admix powder. The spray dryer conditionswere:

Atomization Pressure: 3 Bar

Inlet temperature: 120° C.

Outlet temperature: 50-56° C.

Feeding rate: 5.8 ml/min

2.1 g of the admix powder was then placed into a canister with apre-formed cemented WC substrate to form a pre-sinter assembly, whichwas then loaded into a press and subjected to an ultra-high pressure anda temperature at which the super hard material is thermodynamicallystable to sinter the super hard grains. The pressure to which theassembly was subjected was about 6.8 GPa and the temperature was atleast about 1,200 degrees centigrade. The sintered PCD construction wasthen removed from the canister.

A conventional PCD cutter construction formed of the same mixture ofdiamond grain sizes (grades) as set out in the above example, butwithout adding the nano-ceramic material was prepared in a conventionalmanner for forming PCD by mixing using conventional milling and mixingtechniques and the mixture was sintered with a pre-formed cementedcarbide substrate under the same conditions as above for the examplecontaining the nano-ceramic additions.

The prepared PCD constructions formed according to the above methodswere compared in a vertical boring mill test. The results are shown inFIG. 4.

The first PCD construction tested was that formed of the conventionaldiamond grain mixture (without any nano-ceramic additions) and theresults are shown in FIG. 4 by line 100. The second PCD constructiontested was a first example formed with the nano-cBN additions describedabove and the results are shown in FIG. 4 by line 200.

In this test, the wear flat area was measured as a function of thenumber of passes of the construction boring into the workpiece and theresults obtained are illustrated graphically in FIG. 4.

The results provide an indication of the total wear scar area plottedagainst cutting length. It will be seen that the PCD construction formedaccording to the example (line 200) was able to achieve a significantlygreater cutting length than that occurring in the conventional PCDcompact (shown by line 100 in FIG. 4) which was subjected to the sametest for comparison and the PCD construction formed according to theexample (line 200) was able to achieve a smaller wear scar area thanthat occurring in the conventional PCD compact (shown by line 100 inFIG. 4).

Thus it will be seen from FIG. 4 that the PCD construction formed withthe inclusion of nano-ceramic material in the admix in the mannerdescribed above from a homogeneously distributed solution to enable thenano-ceramic to coat the larger diamond grains as shown in FIG. 3 priorto sintering showed an improvement in cutting distance and abrasionresistance over the conventional PCD construction (line 100).

EXAMPLE 2

3 g of nano WC having an average particle size of less than around 100nm was suspended in 15 ml of ethanol and the suspension was treated withsonication probe for at least 15 minutes to thoroughly disperse the nanoWC. In a separate beaker, 1 g of B90 was dissolved into 20 ml ethanol,and then mixed with the nano WC dispersion. The mixture was concentratedto 20 ml by evaporating the excess amount of ethanol in a Rotavap.Following the concentration, 5 ml of deionized water was introduced intothe ethanol concentration and the nano WC together with B90 wasprecipitated out of the ethanol solution to form nano clusters of nanoWC having an average cluster size of around 1200 nm.

In a separate beaker, 67.9 g of diamond grains having an average grainsize of around 22 microns (Grade 22) was suspended in 30 ml deionizedwater and the nano clusters of nano WC solution were then introducedinto the suspension. The mixture was gently stirred with an overheadstirrer for at least half an hour to obtain nano clusters of nano WCcoated diamond.

In a separate beaker, 2 g of SP cobalt and 1 g of surfactant was mixedwith 20 ml of deionized water, and subjected to a sonication processwith ultrasonic probe for 15 minutes. 29.1 g of diamond grains having anaverage grain size of around 2 microns (Grade 2) was introduced into thesuspension and the suspension was subjected to a sonication process fora further 5 minutes. This suspension was then introduced into thesuspension comprising the diamond grains having an average grain size of22 microns (grade 22) and the resulting mixture was gently stirred withan overhead stirrer for 10 minutes to form a final admix suspension. Thefinal admix suspension was spray dried with a BUCHI Mini-290 spray dryerto remove liquids and form an admix powder. The spray dryer conditionswere:

Atomization Pressure: 3 Bar

Inlet temperature: 120° C.

Outlet temperature: 50-56° C.

Feeding rate: 5.8 ml/min

2.1 g of the admix powder comprising around 3 wt % WC nano-clusters wasthen placed into a canister with a pre-formed cemented WC substrate toform a pre-sinter assembly, which was then loaded into a press andsubjected to an ultra-high pressure and a temperature at which the superhard material is thermodynamically stable to sinter the super hardgrains. The pressure to which the assembly was subjected was about 6.8GPa and the temperature was at least about 1,200 degrees centigrade. Thesintered PCD construction was then removed from the canister.

A conventional PCD cutter construction formed of the same mixture ofdiamond grain sizes (grades) as set out in the above example, butwithout adding the nano-ceramic material was prepared in a conventionalmanner for forming PCD by mixing using conventional milling and mixingtechniques and the mixture was sintered with a pre-formed cementedcarbide substrate under the same conditions as above for the examplecontaining the nano-ceramic additions.

The prepared PCD constructions formed according to the above methodswere compared in a vertical boring mill test. The results are shown inFIG. 5.

The first PCD construction tested was that formed of the conventionaldiamond grain mixture (without any nano-ceramic additions) and theresults are shown in FIG. 5 by line 500. The second PCD constructiontested was a first example formed with the nano-WC additions describedabove and the results are shown in FIG. 5 by line 600. A third PCDconstruction was also tested which was a further example formed with thenano-WC additions described above to test repeatability and the resultsare shown in FIG. 5 by line 700. All samples tested in the test whoseresults are shown in FIG. 5 were in the unleached state, that is, thesamples had not been subjected to a post synthesis treatment to removeresidual binder catalyst from the interstices.

As shown in FIG. 5, the two example constructions (600, 700) showed noreduction on abrasive resistance compared to the conventional PCDconstruction in the unleached state.

An additional sample according to example 2 was produced as was anadditional reference cutter which was formed of the same mixture ofdiamond grain sizes (grades) as set out in the above example 2, butwithout adding the nano-ceramic material, and it was prepared in aconventional manner for forming PCD by mixing using conventional millingand mixing techniques and the mixture was sintered with a pre-formedcemented carbide substrate under the same conditions as above for theexample containing the nano-ceramic additions. The constructions werethen subjected to an acid leaching treatment to remove residual catalystbinder from the interstices. The treated PCD constructions were thencompared in a further vertical boring mill test. The results are shownin FIG. 6.

In this test, the wear flat area was measured as a function of thenumber of passes of the construction boring into the workpiece and theresults obtained are illustrated graphically in FIG. 6.

The results provide an indication of the total wear scar area plottedagainst cutting length. It will be seen that the PCD construction formedaccording to the example (line 800) was able to achieve a significantlygreater cutting length than that occurring in the conventional PCDcompact (shown by line 900 in FIG. 6) which was subjected to the sametest for comparison and the PCD construction formed according to theexample (line 800) was able to achieve a smaller wear scar area thanthat occurring in the conventional PCD compact (shown by line 900 inFIG. 6).

Thus it will be seen from FIG. 6 that the leached PCD constructionformed with the inclusion of nano-ceramic material in the admix in themanner described above from a homogeneously distributed solution toenable the nano-ceramic to coat the larger diamond grains as shown inFIG. 3 prior to sintering showed an improvement in cutting distance andabrasion resistance over the conventional PCD construction (line 900).

Whilst not wishing to be bound by a particular theory, it is believedthat the fracture performance of PCD may be improved through theintroduction of a nano-sized second phase comprising hard ceramicmaterials which may not chemically react with the super hard grains,and/or may not inter-grow. The second phase, particularly those formedof a cluster of nano particles, are believed to promote crackbifurcation or multiple crack fronts in the PCD material in use,resulting in a redistribution of available strain energy or energyrelease rate (G) amongst the various crack tips, and/or favourablydivert cracks in the PCD material. A material that is able to generatemultiple cracks under loading would behave tougher than a material withonly one major crack since multiple crack fronts ensures that the netenergy supplied to the material is divided between several cracks,resulting in a much slower rate of crack growth through the material.The end result in application of the PCD material including suchmicro-defects is that, in use, the number of cracks initiated on thewear scar may be increased as compared to conventional PCD, thusreducing the strain energy available for each individual crack, henceslowing the growth rate, and the generation of shorter cracks. The idealcase is where the wear rate is comparable to the crack growth rate, inwhich case no cracks will be visible behind the wear scar therebyforming a smooth wear scar appearance with no chips or grains pulled outof the sintered PCD.

The addition of such a second phase may also have the effect ofincreasing the thermal stability of the PCD through the resultant lowercobalt content in the material of the examples compared to conventionalPCD.

The size, shape and distribution of these second phase particles,grains, clusters, granules or agglomerates may be tailored to the finalapplication of the PCD material. It is believed possible to improvefracture resistance without significantly compromising the overallabrasion resistance of the material, which is desirable for PCD cuttingtools.

Thus, it is believed that one or more examples may provide a means oftoughening PCD material without compromising its high abrasionresistance and may assist in enabling the creation of multiplecrack-fronts or defects which may help to redistribute or dissipate theavailable fracture energy. These defects may also promote crackbifurcations, which is another energy dissipation mechanism. The endresult is that there may be insufficient energy available to eachindividual crack to enable it to propagate quickly and hence this maysignificantly slow down the rate of crack growth.

The vertical borer test results of these engineered structures show aconsiderable increase in PCD cutting tool life compared to conventionalPCD, and with no degradation in abrasion resistance.

Observation of the wear scar development during testing showed theexample material's ability to generate large wear scars withoutexhibiting brittle-type micro-fractures (e.g. spalling or chipping),leading to a longer tool life.

Thus, examples of a PCD material may be formed having that a combinationof high abrasion and fracture performance.

The microstructure of the PCD constructions formed according to one ormore of the above described example methods may be determined usingconventional image analysis techniques such as scanning electronmicrographs (SEM) taken using a backscattered electron signal.

The homogeneity or uniformity of the PCD structure may be quantified byconducting a statistical evaluation using a large number of micrographsof polished sections. The distribution of the filler phase, which iseasily distinguishable from that of the diamond phase using electronmicroscopy, can then be measured in a method similar to that disclosedin EP 0 974 566 (see also WO2007/110770). This method allows astatistical evaluation of the average thicknesses of the binder phasealong several arbitrarily drawn lines through the microstructure. Thisbinder thickness measurement is also referred to as the “mean free path”by those skilled in the art.

While various versions have been described with reference to a number ofexamples, those skilled in the art will understand that various changesmay be made and equivalents may be substituted for elements thereof andthat these examples are not intended to limit the particular examples orversions disclosed.

For example, in some embodiments of the method, the PCD material may besintered for a period in the range from about 1 minute to about 30minutes, in the range from about 2 minutes to about 15 minutes, or inthe range from about 2 minutes to about 10 minutes.

In some examples of the method, the sintering temperature may be in therange from about 1,200 degrees centigrade to about 2,300 degreescentigrade, in the range from about 1,400 degrees centigrade to about2,000 degrees centigrade, in the range from about 1,450 degreescentigrade to about 1,700 degrees centigrade, or in the range from about1,450 degrees centigrade to about 1,650 degrees centigrade.

In one example, the method may include removing residual metalliccatalyst/binder material for diamond from interstices between thediamond grains of the PCD material. In some examples, the PCD structuremay have a region adjacent a surface comprising at most about 2 volumepercent of catalyst material for diamond. In further examples, the PCDstructure may additionally have a region remote from the surfacecomprising greater than about 2 volume percent of catalyst material fordiamond. In some such examples, the region adjacent the surface mayextend to a depth of at least about 20 microns, at least about 80microns, at least about 100 microns or even at least about 400 micronsfrom the surface, or greater.

1. A knob adapted for insertion into the hollow end of a sports stick, the knob comprising a central longitudinal axis, a tang for insertion into the hollow end of the sports stick, a grip adapted for being grasped by the hand of an athlete, and a step between the tang and the grip adapted for abutting the end surface of the hollow end of the sports stick when the tang is inserted therein, the grip comprising a grip end distal to the tang, a dorsal cantle region and a ventral cantle region, the dorsal and ventral cantle regions being between the tang and the grip end and on opposing sides of an imaginary coronal plane containing the central longitudinal axis and divided by an imaginary sagittal plane that contains the central longitudinal axis and is orthogonal to the imaginary coronal plane, the dorsal and ventral cantle regions each providing a curved support surface for the hand of the athlete when the athlete is gripping the sports stick, the dorsal cantle region and the ventral cantle region each having a radius of curvature in the sagittal plane, the radius of curvature of the ventral cantle region being greater than the radius of curvature of the dorsal cantle region.
 2. The knob of claim 1 wherein a ratio of the radius of curvature of the ventral cantle region to the radius of curvature of the dorsal cantle region is (i) at least 2:1, respectively; or (ii) at least 3:1, respectively, or (iii) at least 5:1, respectively. 3-4. (canceled)
 5. The knob of claim 1 wherein a ratio of the radius of curvature of the ventral cantle region to the radius of curvature of the dorsal cantle region is (i) less than 20:1; or (ii) less than 15:1; or (iii) less than 10:1. 6-7. (canceled)
 8. The knob of claim 1 wherein the imaginary sagittal plane bisects each of the dorsal and the ventral cantle regions into symmetrical halves, respectively.
 9. A knob adapted for insertion into the hollow end of a sports stick, the knob comprising a central longitudinal axis, a tang for insertion into the hollow end of the sports stick, a grip adapted for being grasped by the hand of an athlete, and a step between the tang and the grip adapted for abutting the end surface of the hollow end of the sports stick when the tang is inserted therein, the grip comprising a grip end distal to the tang, a dorsal cantle region and a ventral cantle region, the dorsal and ventral cantle regions being between the tang and the grip end and on opposing sides of an imaginary coronal plane containing the central longitudinal axis and bisected by an imaginary sagittal plane that contains the central longitudinal axis and is orthogonal to the imaginary coronal plane, the dorsal and ventral cantle regions each providing a curved support surface for the hand of the athlete when the athlete is gripping the sports stick, wherein the dorsal cantle region and ventral cantle region are asymmetric relative to each other about the coronal plane and the sagittal plane bisects each of the ventral and the dorsal cantle regions into symmetrical halves, respectively.
 10. The knob of claim 1 wherein the ventral cantle region smoothly transitions about the central longitudinal axis to the dorsal cantle region.
 11. The knob of claim 1 wherein the grip end has a circumference that (i) is at least 110% of the circumference of the neck; or (ii) at least 150% of the circumference of the neck; or (iii) at least 200% of the circumference of the neck; or (iv) at least 300% of the circumference of the neck. 12-14. (canceled)
 15. The knob of any of claim 1 wherein the tang has a length measured along the central longitudinal axis of about 2 to about 12 inches, and optionally wherein the tang has an end that is beveled at an angle of about 30° to 60° from the longitudinal sides of the tang and toward the longitudinal central axis to allow for easier initial guided insertion of the tang into the hollow end of the stick.
 16. (canceled)
 17. The knob of claim 1 wherein (i) the grip has a length, as measured along central longitudinal axis 1.2, that is about 5 to about 95% of the length of the knob and the tang has a complementary length, as measured along the central longitudinal axis, that is about 95 to about 5% of the length of the knob; or (ii) the grip has a length, as measured along central longitudinal axis 1.2, that is about 15 to about 85% of the length of the knob and the tang has a complementary length, as measured along the central longitudinal axis, that is about 85 to about 15% of the length of the knob; or (iii) the grip has a length, as measured along central longitudinal axis 1.2, that is about 25 to about 75% of the length of the knob and the tang has a complementary length, as measured along the central longitudinal axis, that is about 75 to about 25% of the length of the knob; or (iv) the grip has a length, as measured along central longitudinal axis 1.2, that is about 35 to about 65% of the length of the knob and the tang has a complementary length, as measured along the central longitudinal axis, that is about 65 to about 35% of the length of the knob; or (v) the grip has a length, as measured along central longitudinal axis 1.2, that is about 40 to about 60% of the length of the knob and the tang has a complementary length, as measured along the central longitudinal axis, that is about 60 to about 40% of the length of the knob. 18-21. (canceled)
 22. The knob of claim 1 wherein the grip comprises a neck between the flange and the tang.
 23. The knob of claim 22 wherein (i) the neck has a length measured along the central longitudinal axis of at least about 0.25 inches, or (ii) the neck has a length measured along the central longitudinal axis in the range of about 0.25 to about 4 inches, or (iii) the neck has a length measured along the central longitudinal axis in the range of about 1 to about 4 inches, or (iv) the neck has a length measured along the central longitudinal axis in the range of about 1 to about 2 inches. 24-26. (canceled)
 27. The knob of claim 1 wherein (i) the knob comprises a ceramic, metal, polymer, composite, wood or a composite or laminate thereof, or (ii) the knob comprises a ceramic, metal, polymer, composite, or a composite or laminate thereof.
 28. (canceled)
 29. A combination of a sport stick and a knob, the knob corresponding to the knob of claim 1 and being inserted into a hollow end of the sport stick.
 30. The combination of claim 29 wherein (i) the sport stick is a hockey stick, a lacrosse stick, a golf club, or a baseball bat; or (ii) the sport stick is a hockey stick, a lacrosse stick, or a golf club.
 31. (canceled)
 32. A combination of a hockey stick and a knob, the knob corresponding to the knob of claim 1 and being inserted into a hollow end of the hockey stick wherein the ventral cantle region of knob is on the same side of the hockey stick as the blade of the hockey stick.
 33. A combination of (i) a lacrosse stick and a knob, the knob corresponding to the knob of claim 1 and being inserted into a hollow end of the lacrosse stick wherein the ventral cantle region of knob is on the same side of the lacrosse stick as the net-side of the head of the lacrosse stick; or (ii) a golf club and a knob, the knob corresponding to the knob of claim 1 and being inserted into a hollow end of the golf club wherein the ventral cantle region of knob and the head of the golf club are on the same side of the imaginary sagittal plane and the dorsal cantle region and the head of the golf club are on opposite sides of the imaginary sagittal plane; or (iii) a combination of a baseball bat and a knob, the knob corresponding to the knob of any of claims 1-28 and being inserted into a hollow end of the baseball bat wherein the tang and step have a circular cross-section. 34-35. (canceled)
 36. The combination of claim 33 wherein the knob comprises a cavity at grip end of the knob sized to accommodate a motion sensor.
 37. The combination of claim 33 wherein the knob comprises a cavity at grip end of the knob sized to accommodate a motion sensor, and the combination further comprises an electronic motion sensor housed in the cavity.
 38. The combination of claim 29 wherein the knob is securely affixed to the sports stick, optionally by welding, screws, nails, staples, glue, adhesive, heat-activated glue, or epoxy.
 39. (canceled) 